Crystalline Monolayer Research Articles

Thermodynamically Stable Synthesis of Large-Scale and Highly Crystalline Transition Metal Dichalcogenide Monolayers and their Unipolar n-n Heterojunction Devices.

Transition metal dichalcogenide (TMDC) monolayers are considered to be potential materials for atomically thin electronics due to their unique electronic and optical properties. However, large-area and uniform growth of TMDC monolayers with large grain sizes is still a considerable challenge. This report presents a simple but effective approach for large-scale and highly crystalline molybdenum disulfide monolayers using a solution-processed precursor deposition. The low supersaturation level, triggered by the evaporation of an extremely thin precursor layer, reduces the nucleation density dramatically under a thermodynamically stable environment, yielding uniform and clean monolayer films and large crystal sizes up to 500 µm. As a result, the photoluminescence exhibits only a small full-width-half-maximum of 48 meV, comparable to that of exfoliated and suspended monolayer crystals. It is confirmed that this growth procedure can be extended to the synthesis of other TMDC monolayers, and robust MoS2 /WS2 heterojunction devices are easily prepared using this synthetic procedure due to the large-sized crystals. The heterojunction device shows a fast response time (≈45 ms) and a significantly high photoresponsivity (≈40 AW-1 ) because of the built-in potential and the majority-carrier transport at the n-n junction. These findings indicate an efficient pathway for the fabrication of high-performance 2D optoelectronic devices.

Molecular Beam Epitaxy of Highly Crystalline Monolayer Molybdenum Disulfide on Hexagonal Boron Nitride.

Atomically thin molybdenum disulfide (MoS2), a direct-band-gap semiconductor, is promising for applications in electronics and optoelectronics, but the scalable synthesis of highly crystalline film remains challenging. Here we report the successful epitaxial growth of a continuous, uniform, highly crystalline monolayer MoS2 film on hexagonal boron nitride (h-BN) by molecular beam epitaxy. Atomic force microscopy and electron microscopy studies reveal that MoS2 grown on h-BN primarily consists of two types of nucleation grains (0° aligned and 60° antialigned domains). By adopting a high growth temperature and ultralow precursor flux, the formation of 60° antialigned grains is largely suppressed. The resulting perfectly aligned grains merge seamlessly into a highly crystalline film. Large-scale monolayer MoS2 film can be grown on a 2 in. h-BN/sapphire wafer, for which surface morphology and Raman mapping confirm good spatial uniformity. Our study represents a significant step in the scalable synthesis of highly crystalline MoS2 films on atomically flat surfaces and paves the way to large-scale applications.

Challenges and Perspectives in the Macromolecular Flatland.

Polymer chemistry has recently welcomed a new addition to its field: the planar macromolecules known as two-dimensional polymers (2DPs). These topologically planar and crystalline monolayer covalent sheets are reminiscent of molecular fishermen's nets and apart from being conceptually very interesting for the field of macro-molecular chemistry, they also show some potential applications as novel 2D materials. This article reviews how the field has developed five years after the first 2DP was synthesised in 2012. After a brief historical introduction, the main synthetic approaches will be discussed providing concrete examples of 2DPs and highlighting the challenges associated with the synthesis and especially structural characterisation of these fascinating macro-molecules. Finally an overview on their potential applications such as membranes for gas separation, rewritable molecular paper and miniaturisation of optical devices will be presented.

Crosslinking of floating colloidal monolayers

Crosslinked colloidal monolayers are promising as templates, lithographic masks, filtration membranes, or membranes for controlled release rates in drug delivery. We demonstrate assembly of monodisperse micron-sized polystyrene (PS) beads at an air/water interface, which are transformed into crystalline monolayers using addition of surface-active agents. Vapor annealing methods with solvents (toluene and xylene) and crosslinking agents (divinylbenzene) were investigated regarding their ability to crosslink these floating monolayers directly at the interface, generating crosslinked membranes with crystal size up to 44 cm2, domain size up to 1.9 mm2, and nano-sized pores (100–300 nm). The demonstrated fabrication method emphasizes short fabrication time using a simple setup.Graphical abstract

A controllable synthesis of uniform MoS2 monolayers on annealed molybdenum foils

Recently, two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted significant interest due to their outstanding electrical and optical properties that arise from the quantum size effect. Although a controllable synthesis of 2D-monolayers is a prerequisite for potential applications, the fabrication of large-scale TMDCs monolayers with spatial homogeneity remains a great challenge. In this letter, we report on an efficient method for the large-scale preparation of molybdenum disulfide (MoS2) by sulfurizing pre-annealed molybdenum foils. Highly crystalline MoS2 monolayers were obtained by sulfurizing annealed Mo foils for 5min at 600°C. This preparation method for fabricating MoS2 monolayer allows the nondestructive transference of the MoS2 layers onto arbitrary substrates. It is believed that the results of this study open a new pathway for the synthesis of large-scale MoS2 monolayers.

Location-specific growth and transfer of arrayed MoS2 monolayers with controllable size

We present a controlled chemical vapor deposition (CVD) growth and transfer of arrayed MoS2 monolayers on predetermined locations. The patterned transition metal oxide (e.g. MoO3) source substrate was contacted face-to-face with an SiO2 growth substrate, where localized MoS2 flakes were synthesized on both source and growth substrates, following a CVD procedure. This growth technique enabled the growth of both single crystalline and polycrystalline MoS2 monolayer arrays with controlled size and location, exclusively on predetermined locations on the growth substrates. As-grown MoS2 arrays were transferred using a unique process that combines the wet and stamping transfer processes and dramatically enhanced the integrity of transferred MoS2 on microstructures, while protecting the microstructures during the transfer process. This fabrication technique can be applied to different transition metal dichalcogenides (TMDs) and allows the formation of TMDs on select locations, potentially eliminating a post-lithography step for device fabrication.

Tuning the Structure and Ionic Interactions in a Thermochemically Stable Hybrid Layered Titanate‐Based Nanocomposite for High Temperature Solid Lubrication

Solid inorganic lubricants are thermally stable but they are often limited by their lack of deformability, while organic lubricants have limitations in terms of thermal stability. In this study, a novel solid organic–inorganic nanocomposite lubricant that synergistically combines the thermochemically stable structure of a layered oxide with the relative softness of an organic polymer is presented. The nanocomposite is made by intercalating 11‐aminoundecanoic acid in a lepidocrocite‐type protonated titanate, H1.07Ti1.73O4. The amino acid molecules rapidly arrange to form a paraffinic bilayer in the gallery region of the layered host. This topotactic reaction yields a well‐organized layered nanocomposite consisting of inorganic 2D titanate layers separated by amino acid molecules. Above elevated temperatures, 11‐undecanoic acid polymerizes into nylon‐11 confined between crystalline titanate monolayers. The lubricating properties of these nanocomposites up to 580 °C are determined using high‐temperature pin‐on‐disc experiments using steel‐steel contacts. The lubricative properties are based on the softening of the intercalated polymer above 200 °C. The encapsulation of the polymer chains by the inorganic titanate monolayers protects the organic component from thermal degradation and increases the thermal stability of the system.

Centimeter-Scale CVD Growth of Highly Crystalline Single-Layer MoS2 Film with Spatial Homogeneity and the Visualization of Grain Boundaries.

MoS2 monolayer attracts considerable attention due to its semiconducting nature with a direct bandgap which can be tuned by various approaches. Yet a controllable and low-cost method to produce large-scale, high-quality, and uniform MoS2 monolayer continuous film, which is of crucial importance for practical applications and optical measurements, remains a great challenge. Most previously reported MoS2 monolayer films had limited crystalline sizes, and the high density of grain boundaries inside the films greatly affected the electrical properties. Herein, we demonstrate that highly crystalline MoS2 monolayer film with spatial size up to centimeters can be obtained via a facile chemical vapor deposition method with solid-phase precursors. This growth strategy contains selected precursor and controlled diffusion rate, giving rise to the high quality of the film. The well-defined grain boundaries inside the continuous film, which are invisible under an optical microscope, can be clearly detected in photoluminescence mapping and atomic force microscope phase images, with a low density of ∼0.04 μm-1. Transmission electron microscopy combined with selected area electron diffraction measurements further confirm the high structural homogeneity of the MoS2 monolayer film with large crystalline sizes. Electrical measurements show uniform and promising performance of the transistors made from the MoS2 monolayer film. The carrier mobility remains high at large channel lengths. This work opens a new pathway toward electronic and optical applications, and fundamental growth mechanism as well, of the MoS2 monolayer.

In Vitro Characterization of the Two-Stage Non-Classical Reassembly Pathway of S-Layers.

The recombinant bacterial surface layer (S-layer) protein rSbpA of Lysinibacillus sphaericus CCM 2177 is an ideal model system to study non-classical nucleation and growth of protein crystals at surfaces since the recrystallization process may be separated into two distinct steps: (i) adsorption of S-layer protein monomers on silicon surfaces is completed within 5 min and the amount of bound S-layer protein sufficient for the subsequent formation of a closed crystalline monolayer; (ii) the recrystallization process is triggered—after washing away the unbound S-layer protein—by the addition of a CaCl2 containing buffer solution, and completed after approximately 2 h. The entire self-assembly process including the formation of amorphous clusters, the subsequent transformation into crystalline monomolecular arrays, and finally crystal growth into extended lattices was investigated by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). Moreover, contact angle measurements showed that the surface properties of S-layers change from hydrophilic to hydrophobic as the crystallization proceeds. This two-step approach is new in basic and application driven S-layer research and, most likely, will have advantages for functionalizing surfaces (e.g., by spray-coating) with tailor-made biological sensing layers.

Temperature-Tuned Faceting and Shape Changes in Liquid Alkane Droplets.

Recent extensive studies reveal that surfactant-stabilized spherical alkane emulsion droplets spontaneously adopt polyhedral shapes upon cooling below a temperature Td while remaining liquid. Further cooling induces the growth of tails and spontaneous droplet splitting. Two mechanisms were offered to account for these intriguing effects. One assigns the effects to the formation of an intradroplet frame of tubules consisting of crystalline rotator phases with cylindrically curved lattice planes. The second assigns the sphere-to-polyhedron transition to the buckling of defects in a crystalline interfacial monolayer, known to form in these systems at some Ts > Td. The buckling reduces the extensional energy of the crystalline monolayer's defects, unavoidably formed when wrapping a spherical droplet by a hexagonally packed interfacial monolayer. The tail growth, shape changes, and droplet splitting were assigned to the decrease and vanishing of surface tension, γ. Here we present temperature-dependent γ(T), optical microscopy measurements, and interfacial entropy determinations for several alkane/surfactant combinations. We demonstrate the advantages and accuracy of the in situ γ(T) measurements made simultaneously with the microscopy measurements on the same droplet. The in situ and coinciding ex situ Wilhelmy plate γ(T) measurements confirm the low interfacial tension, ≲0.1 mN/m, observed at Td. Our results provide strong quantitative support validating the crystalline monolayer buckling mechanism.

Rotational superstructure in van der Waals heterostructure of self-assembled C60 monolayer on the WSe2 surface.

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C60 molecules self-assembled on the surface of WSe2 in well-ordered arrays with large grain sizes (∼5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure in the C60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate-adsorbate and adsorbate-substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. This rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.

Tracking Invisible Transformations of Physisorbed Monolayers: LDI-TOF and MALDI-TOF Mass Spectrometry as Complements to STM Imaging.

Triphenyleneethynylene (TPEE) derivatives bearing one long aliphatic chain on each terminal aryl ring and two short aliphatic chains on the central aryl ring (core chains) self-assemble single component and 1-D patterned, two-component, crystalline monolayers at the solution-graphite interface. The monolayer morphology directs the core chains off the graphite, making them accessible for chemical reactions but invisible to imaging by scanning tunneling microscopy (STM). This precludes using STM to monitor transformations of the core chains, either by reaction or solution-monolayer exchange of TPEE molecules. Laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) successfully identifies TPEE compounds within physisorbed monolayers. The LDI-TOF spectra of TPEE monolayer-graphite samples exhibit strong molecular ion peaks and minimal fragmentation or background. LDI-TOF and STM techniques are combined to evaluate monolayer composition and morphology, track solution-monolayer exchange, to identify reaction products and to measure kinetics of chemical reactions at the solution-monolayer interface. LDI-TOF MS provides rapid qualitative evaluation of monolayer composition across a graphite substrate. Challenges to quantitative composition evaluation by LDI-TOF include compound-specific light absorption, surface desorption/ionization and fragmentation characteristics. For some, but not all, compounds, applying matrix onto a self-assembled monolayer increases molecular ion intensities and affords more accurate assessment of monolayer composition via matrix assisted laser desorption/ionization (MALDI) MS. Matrix addition precludes subsequent chemical or STM studies of the monolayer, whereas reactions and STM may be performed at nonirradiated regions following LDI-TOF measurements. LDI- and MALDI-TOF MS are useful complements to STM and are easily implemented tools for study of physisorbed monolayers.

Achieving Uniform Monolayer Transition Metal Dichalcogenides Film on Silicon Wafer via Silanization Treatment: A Typical Study on WS2.

A silanization reaction is employed to improve the dispersion of precursors on a silicon wafer for a large-size uniform transition metal dichalcogenide (TMD) film synthesis and to achieve a highly crystalline monolayer WS2 film up to 1 cm2 . The novel strategy is also verified for the synthesis of WSe2 and MoS2 uniform films, suggesting universality for TMD film fabrication.

MoS2 based dual input logic AND gate

Crystalline monolayers of CVD MoS2 are used as the active semiconducting channel in a split-gate field effect transistor. The device demonstrates logic AND functionality that is controlled by independently addressing each gate terminal with ±10V. When +10V was simultaneously applied to both gates, the device was conductive (ON), while any other combination of gate voltages rendered the device resistive (OFF). The ON/OFF ratio of the device was ∼ 35 and the charge mobility using silicon nitride as the gate dielectric was 1.2cm2/V-s and 0.1cm2/V-s in the ON and OFF states respectively. Clear discrimination between the two states was observed when a simple circuit containing a load resistor was used to test the device logic AND functionality at 10Hz. One advantage is that split gate technology can reduce the number of devices required in complex circuits, leading to compact electronics and large scale integration based on intrinsic 2-D semiconducting materials.

Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma

Two-dimensional layered transition metal dichalcogenide (TMD) materials such as Molybdenum disufide (MoS2) have been recognized as one of the low-cost and efficient electrocatalysts for hydrogen evolution reaction (HER). The crystal edges that account for a small percentage of the surface area, rather than the basal planes, of MoS2 monolayer have been confirmed as their active catalytic sites. As a result, extensive efforts have been developing in activating the basal planes of MoS2 for enhancing their HER activity. Here, we report a simple and efficient approach—using a remote hydrogen-plasma process—to creating S-vacancies on the basal plane of monolayer crystalline MoS2; this process can generate high density of S-vacancies while mainly maintaining the morphology and structure of MoS2 monolayer. The density of S-vacancies (defects) on MoS2 monolayers resulted from the remote hydrogen-plasma process can be tuned and play a critical role in HER, as evidenced in the results of our spectroscopic and electrical measurements. The H2-plasma treated MoS2 also provides an excellent platform for systematic and fundamental study of defect-property relationships in TMDs, which provides insights for future applications including electrical, optical and magnetic devices.

Truncation Derivatives of the S-Layer Protein of Sporosarcina ureae ATCC 13881 (SslA): Towards Elucidation of the Protein Domain Responsible for Self-Assembly

The cell surface of Sporosarcina ureae ATCC 13881 is covered by an S-layer (SslA) consisting of identical protein subunits that assemble into lattices exhibiting square symmetry. In this work the self-assembly properties of the recombinant SslA were characterised with an emphasis on the identification of protein regions responsible for self-assembly. To this end, recombinant mature SslA (aa 31-1097) and three SslA truncation derivatives (one N-terminal, one C-terminal and one CN-terminal) were produced in a heterologous expression system, isolated, purified and their properties analysed by in vitro recrystallisation experiments on a functionalised silicon wafer. As a result, recombinant mature SslA self-assembled into crystalline monolayers with lattices resembling the one of the wild-type SslA. The study identifies the central protein domain consisting of amino acids 341-925 self-sufficient for self-assembly. Neither the first 341 amino acids nor the last 172 amino acids of the protein sequence are required to self-assemble into lattices.

Molecular Shape and the Hydrophobic Effect.

This review focuses on papers published since 2000 on the topic of the properties of solutes in water. More specifically, it evaluates the state of the art of our understanding of the complex relationship between the shape of a hydrophobe and the hydrophobic effect. To highlight this, we present a selection of references covering both empirical and molecular dynamics studies of small (molecular-scale) solutes. These include empirical studies of small molecules, synthetic hosts, crystalline monolayers, and proteins, as well as in silico investigations of entities such as idealized hard and soft spheres, small solutes, hydrophobic plates, artificial concavity, molecular hosts, carbon nanotubes and spheres, and proteins.

Influence of residual promoter to photoluminescence of CVD grown MoS2

Monolayer MoS2 has attracted extensive attention owing to its promising applications in optoelectronic devices. Recently, uniform and highly crystalline monolayer MoS2 was grown through chemical vapor deposition (CVD) using seed materials as a growth promoter. However, residual seed materials can remain on the surface of a monolayer MoS2 flake on a SiO2/Si substrate after growth. Here, we observe drastically increased photoluminescence (PL) intensity at the edge of MoS2 flake where residual particles are attached after repeated laser irradiation. On the other hand, the PL intensity of pure MoS2 remained almost the same. We attribute this to the effect of p-doping of the edge MoS2 by the adsorbed H2O and O2 molecules in the residual particles. The p-doping effect of MoS2 is confirmed by the confocal PL and Raman spectroscopy analysis.

Horizontally-connected ZnO-graphene hybrid films for multifunctional devices

Here we designed horizontally-connected ZnO thin films and graphene in order to combine advantages of ZnO thin films, which are high on/off ratio and photo responsivity, and the superior mobility and sensitivity of graphene for applications in thin film transistors (TFTs) and flexible photodetectors. To synthesize the ZnO/graphene hybrid films, a 70-nm-thick ZnO thin film with a uniformly flat surface deposited by the atomic layer deposition process was horizontally connected with highly crystalline monolayer graphene grown by thermal chemical vapor deposition. The photocurrent on-off ratio, response time, and recovery time of the hybrid photodetectors were estimated to be 102, 34s, and 27s, respectively. The photocurrent from the hybrid photodetector decreased only by two-fold, whereas a significant decrease in photocurrent by two orders of magnitude was observed from the ZnO thin film based photodetectors after 105 cycles of 5-mm radius bending. The hybrid TFT exhibited unipolar n-channel transistor behavior with electron mobility of 68.7cm2/Vs and on-off ratio of 107.

Synthesis of high‐quality graphene oxide from spent mobile phone batteries

Synthesis of high‐quality graphene oxide from waste graphite recovered from spent mobile phone batteries was investigated. Graphite powders were easily removed from the anodic copper foil of lithium ion batteries opposed to being sent to landfills. Graphene oxide (GO) was prepared by leaching and oxidation of the graphite with a mixture of potassium permanganate and concentrated sulfuric acid. The structure of GO has been studied using Infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). FT‐IR spectra of GO indicate the existence of –OH, ketone and ‐O‐ groups. Crystalline monolayer and multilayer nano‐sized structures of exfoliated graphene oxide sample exhibiting atomically smooth edges were observed by SEM and TEM. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 1485–1491, 2016